Hydrofluorination of 1233xf to 244bb by sbf5

ABSTRACT

The disclosure relates to a method for hydrofluorination of an olefin of the formula: RCX═CYZ to produce a hydrofluoroalkane of formula RCXFCHYZ or RCXHCFYZ, wherein X, Y, and Z are independently the same or different and are selected from the group consisting of H, F, Cl, Br, and C 1 -C 6  alkyl which is partially or fully substituted with chloro or fluoro or bromo; and R is a C 1 -C 6  alkyl which is unsubstituted or substituted with chloro or fluoro or bromo, comprising reacting the olefin with HF in the liquid-phase, in the presence of SbF 5 , at a temperature ranging from about −30° C. to about 65° C. and compositions formed by the process.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.15/575,526 filed Nov. 20, 2017, allowed, which is a 371 National StageApplication of PCT/US2016/033450 filed May 20, 2016, which claims thebenefit of and priority to U.S. Provisional Application No. 62/164,631filed May 21, 2015, which are hereby incorporated by reference in theirentirety.

BACKGROUND OF THE INVENTION

This disclosure relates to novel methods for preparing fluorinatedorganic compounds, and more particularly to methods of producingfluorinated hydrocarbons.

Hydrofluorocarbons (HFCs), in particular hydrofluoroalkenes orfluoroolefins, such as tetrafluoropropenes (including2,3,3,3-tetrafluoro-1-propene (HFO-1234yf or 1234yf)) have beendisclosed to be effective refrigerants, fire extinguishants, heattransfer media, propellants, foaming agents, blowing agents, gaseousdielectrics, sterilant carriers, polymerization media, particulateremoval fluids, carrier fluids, buffing abrasive agents, displacementdrying agents and power cycle working fluids. Unlike chlorofluorocarbons(CFCs) and hydrochlorofluorocarbons (HCFCs), both of which potentiallydamage the Earth's ozone layer, HFCs do not contain chlorine and, thus,pose no threat to the ozone layer.

In addition to ozone depleting concerns, global warming is anotherenvironmental concern in many of these applications. Thus, there is aneed for compositions that meet both low ozone depletion standards aswell as having low global warming potentials. Certain fluoroolefins arebelieved to meet both goals. Thus, there is a need for manufacturingprocesses that provide halogenated hydrocarbons and fluoroolefins thatcontain no chlorine that also have a low global warming potential.

One such HFO is 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf or 1234yf).The preparation of HFO-1234yf starting from CQ₂=CCl—CH₂Q or CQ₃-CCl═CH₂or CQ₃-CHCl—CH₂Q may include three reaction steps, as follows:

(i) (CQ₂₌CCl—CH₂Q or CQ₃-CCl═CH₂ orCQ₃-CHCl—CH₂Q)+HF→2-chloro-3,3,3-trifluoropropene (HCFO-1233xf or1233xf)+HCl in a vapor phase reactor charged with a solid catalyst;

(ii) 2-chloro-3,3,3-trifluoropropene(HCFO-1233xf)+HF→2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb or244bb) in a liquid phase reactor charged with a liquid hydrofluorinationcatalyst; and

-   -   (iii) 2-chloro-1,1,1,2-tetrafluoropropane        (HCFC-244bb)→2,3,3,3-tetrafluoropropene (HFO-1234yf) in a vapor        phase reactor; wherein Q is independently selected from F, Cl,        Br, and I, provided that at least one Q is not fluorine.

The hydrofluorination of 1233xf to 244bb is usually conducted in thepresence of fluorinated SbCl₅ at temperatures above 70° C.; otherwisethe catalyst will freeze. Under these conditions, the 1233xf is notcompletely converted to 244bb because of equilibrium limitations,especially at higher temperatures. As a result, significant amounts of1233xf are present in the product formed. Since the boiling points of1233xf and 244bb are only about 2° C. apart, separation of these twospecies is difficult and expensive.

Moreover, the presence of 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf)in the reaction starting materials, such as HCFC-244bb feedstock, canlead to dramatically reduced conversion of HCFC-244bb to HFO-1234yf. Inaddition, the 2-chloro-3,3,3-trifluoropropene copresence in the startingmaterial, when subjected to dehydrochlorination, can lead to theformation of trifluoropropyne and oligomers, which can produce tar. Thisresult is disadvantageous from the standpoint of a reduced yield of thedesired product. Therefore, there is a need for a better catalyticreaction to achieve a higher conversion of 1233xf to 244bb to avoidand/or minimize the need for purification.

The present invention fulfills that need.

SUMMARY OF THE INVENTION

The disclosure relates to a method for hydrofluorination of an olefin ofthe formula: RCX═CYZ to produce hydrofluoroalkanes of formula RCXFCHYZand RCHXCFYZ, wherein X, Y and Z are independently the same or differentand are selected from the group consisting of H, F, Cl, Br, and C1-C6alkyl which is partly or fully substituted with chloro or fluoro orbromo, and R is a C₁-C6 alkyl which is partially or fully substitutedwith chloro or fluoro or bromo, comprising reacting the fluoroolefinwith HF in the liquid-phase, in the presence of SbF₅, at a temperatureranging from about −30° C. to about 65° C.

DETAILED DESCRIPTION OF THE INVENTION

The foregoing general description and the following detailed descriptionare exemplary and explanatory only and are not restrictive of theinvention.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B is true (orpresent).

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. In case of conflict, thepresent specification, including definitions, will control. Althoughmethods and materials similar or equivalent to those described hereincan be used in the practice or testing of embodiments of the presentinvention, suitable methods and materials are described below. Inaddition, the materials, methods, and examples are illustrative only andnot intended to be limiting.

The term “olefin”, as used herein refers to a compound containing acarbon-carbon double bond. It is defined herein relative to the formulaRCX═CYZ.

The terms “hydrofluoroalkene” or “fluoroolefin”, as used herein, denotesa compound containing hydrogen, carbon, fluorine, and at least onecarbon-carbon double bond and optionally chlorine.

“HFO”, as used herein, indicates a compound containing hydrogen, carbon,fluorine, and at least one carbon-carbon double, and no chlorine.“HCFO”, as used herein, indicates a compound containing hydrogen,carbon, chlorine, fluorine, and at least one carbon-carbon double.“HCO”, as used herein, indicates a compound containing hydrogen, carbon,chlorine, and at least one carbon-carbon double bond, and no fluorine.

The term “hydrofluorination” is understood to mean the addition reactionof hydrogen fluoride to a carbon-carbon double bond.

The term “hydrofluoroalkane”, as used herein, refers to an alkane havingtwo or more carbon atoms containing hydrogen, fluorine, and optionallychlorine, whereby a fluorine atom and a hydrogen atom are substituted ontwo adjacent carbon atoms. As used herein, the hydrofluoroalkane can bethe product from the hydrofluorination of the fluoroolefin.

The HF used herein is an anhydrous liquid hydrogen fluoride which iscommercially available or it may be a gas that is bubbled into thereactor. Anhydrous HF is sold by, for example, Solvay S.A, The ChemoursCompany FC, LLC and Honeywell International, Inc.

As used herein, the term “conversion” with respect to a reactant, whichtypically is a limiting agent, refers to the number of moles reacted inthe reaction process divided by the number of moles of that reactantinitially present in the process multiplied by 100.

As used herein, percent conversion is defined as 100%, less the weightpercent of starting material in the effluent from the reaction vessel.

As used herein, the term “selectivity” with respect to an organicreaction product refers to the ratio of the moles of that reactionproduct to the total of the moles of the organic reaction productsmultiplied by 100.

As used herein, “percent selectivity” is defined as the weight of adesired product formed, as a fraction of the total amount of theproducts formed in the reaction, and excluding the starting material.

Some fluoroolefins of this disclosure, e.g., CF₃CH═CHCl (HCFO-1233zd or1233zd), exist as different configurational isomers or stereoisomers.When the specific isomer is not designated, the present disclosure isintended to include all single configurational isomers, singlestereoisomers, or any combination thereof. For instance, HCFO-1233zd ismeant to represent the E-isomer, Z-isomer, or any combination or mixtureof both isomers in any ratio.

Described is a method for producing hydrofluoroalkanes of formulaRCXFCHYZ, wherein X, Y and Z may independently be the same or differentand are selected from H, F, Cl and an alkyl group having 1 to 6 carbonatoms, which alkyl group is partially or fully substituted with fluorineor chlorine; and R is an alkyl group having 1 to 6 carbon atoms, whichalkyl group is partially or fully substituted with fluorine or chlorinecomprising reacting a fluoroolefin of the formula RCX═CYZ with HF in theliquid-phase, in the presence of a catalytic effective amount ofSbF_(5.)

The terms “alkyl group is partially or fully substituted with chlorine”and “chlorinated alkyl” are synonymous and it is meant that the alkylgroup must be at least monosubstituted with Cl. Similarly, the terms“alkyl group is partially or fully substituted with fluorine” and“fluorinated alkyl” are synonymous and it is meant that the alkyl groupmust be at least monosubstituted with F. However, in both cases, thealkyl group may have one or more fluoro substituents thereon or one ormore chloro substituents thereon or a combination of one or more chloroor fluoro groups thereon. Some of the carbon atoms may be substitutedwith one or more chloro or fluoro atoms. In an embodiment, the alkylgroup is substituted with one or more fluoro atoms. In an embodiment,the alkyl group is fully substituted with chloro or fluoro orcombination of both chloro and fluoro. In another embodiment, the alkylgroup is perchlorinated, while in another embodiment, the alkyl group isperfluorinated.

The alkyl group may be branched or linear. In an embodiment, the alkylgroup is linear. In an embodiment, the alkyl group contains 1-4 carbonatoms, and in another embodiment, it contains 1 or 2 or 3 carbon atomsand in still another embodiment 1 or 2 carbon atoms. In anotherembodiment, it contains only 1 carbon atom. Examples include methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

As defined herein, the carbon atoms which are part of the carbon-carbondouble bond are substituted with R, X, Y, and Z. R is defined, amongother things, as being partially or fully substituted with chloro orfluoro and X, Y, or Z may be, among other things, partially or fullysubstituted with chloro or fluoro. In one embodiment, X, Y, Z areindependently partially or fully substituted with chloro or fluoro, andin another embodiment, two of X, Y, and Z are partially or fullysubstituted with chloro or fluoro, and in another embodiment, one of X,Y, and Z is partially or fully substituted with chloro or fluoro, instill another embodiment, three of X, Y and Z are partially or fullysubstituted with chloro or fluoro, and in another embodiment, none of X,Y, Z are partially or fully substituted with chloro or fluoro. Withrespect to X, Y, and Z, when defined as partially or fully substitutedwith chloro or fluoro, and with respect to R, in an embodiment, at leastone carbon atom alpha or beta to the carbon atom bearing the double bond(if alkyl group contains 2 or more carbon atoms) is substituted withchloro or fluoro.

In one embodiment, X, Y, and Z are independently H or fluoro or chloro.In another embodiment, R is perchlorinated or perfluorinated. In someembodiments of this invention, R is —CF₃ or —CF₂CF₃. In anotherembodiment, X, Y, and Z are independently H or fluoro or chloro and R isperfluorinated or perchlorinated. In still further embodiment, X, Y, Zare independently H or fluoro or chloro and R is perfluorinated, forexample, —CF₃ or —CF₂CF₃.

The process according to the invention can be carried out in any reactormade of a material that is resistant to reactants employed, especiallyto hydrogen fluoride. As used herein, the term “reactor” refers to anyvessel in which the reaction may be performed in either a batchwisemode, or in a continuous mode. Suitable reactors include tank reactorvessels with and without agitators, or tubular reactors.

In one embodiment, the reactor is comprised of materials which areresistant to corrosion including stainless steel, Hastelloy, Inconel,Monel, gold or gold-lined or quartz. In another embodiment, the reactoris TFE or PFA-lined.

The olefin described herein has the formula RCX═CYZ, where R, X, Y, Zare as defined hereinabove. Examples include RCCl═CH₂, RCH═CHCl,RCCl═CHCl, RCH═CCl₂ and RCH═CH₂, and the like. In one embodiment, R istrifluoromethyl and in another embodiment, R is pentafluoroethyl.Representative olefins include 2-chloro-3,3,3-trifluoropropene(HCFO-1233xf), 1-chloro-3,3,3-trifluooropropene (HCFO-1233zd),chlorotetrafluoropropenes (HCFO-1224 or 1224),2,3,3,3-tetrafluoropropene (1234yf), dichlorotetrafluoropropenes(HCFO-1214 or 1214), 1,3,3,3-tetrafluoropropene (1234ze),3,3,3-trifluoropropene (HFO-1243zf or 1234zf), and the like.

The hydrofluoroalkanes described herein are the addition products of HFto the fluoroolefins, as defined hereinabove. As defined herein, theyhave the formula RCXFCHYZ or RCXHCFYZ, wherein R, X, Y, Z are as definedhereinabove. As described hereinabove, in one embodiment, R istrifluoromethyl and in another embodiment, R is pentafluoroethyl.Representative hydrofluoropropanes include1,1,1,2-tetrafluoro-2-chloropropane,1,1,1,3-tetrafluoro-3-chloropropane,1,1,1,3,3-pentafluoro-3-chloropropane,1,1,1,2,2-pentafluoro-3-chloropropane, 1,1,1,2,2-pentafluoropropane,1,1,1,3,3-pentafluoropropane and the like.

The present process adds HF across the double bond of the fluoroolefinto produce a hydrofluoroalkane. The F atom may add to an internal orterminal carbon atom and the hydrogen atom may add to a terminal orinternal carbon atom. Thus, for example, in accordance with the presentdisclosure, when the fluoroolefin is RCCl═CH₂, the product is RCFClCH₃.In another embodiment, when the fluoroolefin is RCH═CHCl, the product isRCH₂CHFCl. In another embodiment, when the fluoroolefin is RCH═CCl₂, thehydrofluoropropane is RCH₂CFCl₂. In yet another embodiment, when thefluoroolefin is RCH═CH₂, the hydrofluoropropanes formed are RCHFCH₃ andRCH₂CH₂F. With respect to the aforementioned examples, in an embodiment,R can be CF₃ or C₂F₆.

In one embodiment, the fluoroolefin is 2-chloro-3,3,3-trifluoropropeneand the hydrofluoroalkane is 2-chloro-1,1,1,2-tetrafluoropropane. Inanother embodiment, the fluoroolefin is 3,3,3-trifluoropropene and thehydrofluoroalkane is 1,1,1,2-tetrafluoropropane and1,1,1,3-tetrafluoropropane. In another embodiment, the fluoroolefin is(Z)- or (E)-1-chloro-3,3,3-tetrafluoropropene and the hydrofluoroalkaneis 3-chloro-1,1,1,3-tetrafluoropropane. In another embodiment, thefluoroolefin is cis- or trans-1,2-dichloro-3,3,3-trifluoropropene andthe hydrofluoroalkane is 1,1,1,2-tetrafluoro-2,3-dichloropropane and1,1,1,3 -tetrafluoro-2,3-dichloropropane. In another embodiment, thefluoroolefin is 2,3,3,3-tetrafluoropropene, and the hydrofluoroalkane is1,1,1,2,2-pentafluoropropane. In yet another embodiment, thefluoroolefin is 1,3,3,3-tetrafluoropropene and the hydrofluoroalkane is1,1,1,3,3-pentafluoropropane.

Without wishing to be bound, it is believed that with respect to HFaddition to a carbon-carbon double bond, the fluorine atom adds to thecarbon atom of the double bond which has the most halogens attachedthereto. Otherwise, without wishing to be bound, the HF is added to thecarbon atom of the double bond in accordance with Markovnikov's rule,i.e., the hydrogen of HF will add to the carbon atom that will form themore stable carbonium ion. Thus, for example, if one of the carbon atomsof the carbon-carbon double bond has more hydrogen atoms substitutedthereon than the other carbon atom of the carbon-carbon double bond, thehydrogen atom of HF will add to the carbon atom having the most hydrogenatoms substituted thereon.

The above process is conducted in the liquid phase. The fluoroolefin aswell as the hydrogen fluoride are liquids at reaction conditions. Sincewater is used to quench the reaction, the amount of water present isminimized. For example, the hydrogen fluoride used is anhydrous. Thehydrogen fluoride can be bubbled in as a gas or added as a liquid intothe liquid fluoroolefin or it may be present in an anhydrous solvent,such as pyridine. Thus, for example, in an embodiment, although notnecessary, the fluoroolefin is dried with a desiccant before being mixedwith HF or the catalyst. By “desiccant,” it is meant any material whichwill absorb water without dissolving in or otherwise contaminating thefluoroolefin being dried, e.g., calcium sulfate or molecular sieves, andthe like. In another embodiment, the reaction can be conducted in aninert atmosphere, such as under nitrogen, helium, argon and the like.However, in an embodiment, the reaction can be conducted in air and inanother embodiment, the reaction is conducted without drying thefluoroolefin.

In an embodiment, when anhydrous liquid HF is used or HF is fed as agas, the reaction is conducted without any solvent in addition to thesolvent in which the anhydrous HF is dissolved. If the HF is fed as agas, such as, being bubbled in as a gas, the reaction may be conductedwithout any solvent present.

In one embodiment, the hydrofluorination reaction is conducted at atemperature ranging from about −30 C to about 65° C. In anotherembodiment, the hydrofluorination reaction is conducted at a temperatureranging from about −10° C. to about 40° C. In another embodiment, thehydrofluorination reaction is conducted at a temperature ranging fromabout 0° C. to about 30° C. In still another embodiment, thehydrofluorination reaction is conducted at a temperature ranging fromabout 0° C. to about 25° C. In another embodiment, the hydrofluorinationreaction is conducted at a temperature ranging from about 5° C. to about25° C. In still another embodiment, the hydrofluorination reaction isconducted at a temperature ranging from about 5° C. to about 20° C.Moreover, the hydrofluorination reaction can be conducted at anytemperature in-between the ranges disclosed hereinabove, and thesetemperatures are contemplated within the scope of the present invention.Thus, the hydrofluorination described hereinabove is conducted in areaction vessel at about −30° C., about −29° C., about −28° C., about−27° C., about −26° C., about −25° C., about −24° C., about −23° C.,about −22° C., about −21° C., about −20° C., about −19° C., about −18°C., about −17° C., about −16° C., about −15° C., about −14° C., about−13° C., about −12° C., about −11° C., about −10° C., about −9°, about−8° C., about −7° C., about −6° C., about −5° C., about −4° C., about−3° C., about −2° C., about −1° C., about 0° C., about 1° C., about 2°C., about 3° C., about 4° C., about 5° C., about 6° C., about 7° C.,about 8° C., about 9° C., about 10° C., about 11° C., about 12° C.,about 13° C., about 14° C., about 15° C., about 16° C., about 17° C.,about 18° C., about 19° C., about 20° C., about 21° C., about 22° C.,about 23° C., about 24° C., about 25° C., about 26° C., about 27° C.,about 28° C., about 29° C., about 30° C., about 31° C., about 32° C.,about 33° C., about 34° C., about 35° C., about 36° C., about 37° C.,about 38° C., about 39° C., about 40° C., about 41° C., about 42° C.,about 43° C., about 44° C., about 45° C., about 46° C., about 47° C.,about 48° C., about 49° C., about 50° C., about 51° C., about 52° C.,about 53° C., about 54° C., about 55° C., about 56° C., about 57° C.,about 58° C., about 59° C., about 60° C., about 61° C., about 62° C.,about 63° C., about 64° C. or about 65° C.

In an embodiment, the reaction mixture is stirred using techniques knownin the art. For example, the reaction mixture is spun using a stirringbar. Alternatively, the reactor in which the reaction takes place isequipped with an impeller or other stirring device which stirs thereaction mixture.

In another embodiment, mixing may be provided by alternatives tostirring devices. Such methods are known in the industry and includeusing the mixing provided by gas bubbles from gas added to the vessel orgenerated within the vessel by vaporization of liquid. Mixing can alsobe provided by withdrawing the liquid from the vessel to a pump andpumping the liquid back into the vessel. A static mixer or other deviceintended to mix the contents can be present in the circulation path ofthe liquid to provide additional mixing power input.

In one embodiment, the mole ratio of HF to fluoroolefin ranges fromabout 0.5 to about 20. In another embodiment, the mole ratio of HF tofluoroolefin is from about 1 to about 10. In another embodiment, themole ratio of HF to fluoroolefin is from about 1 to about 5.

The SbF₅ is present in catalytic effective amounts. In one embodiment,the SbF₅ catalyst is present from about 1% to about 50% by weight of themixture. In another embodiment, the SbF₅ catalyst is present from about2% to about 30% by weight. In another embodiment, the SbF₅ catalyst ispresent from about 3% to about 15% by weight.

As described hereinabove, hydrofluoroalkanes are prepared by catalyticfluorination of the fluoroolefin. In one embodiment, the catalyticfluorination of the fluoroolefin results in a percent conversion to thehydrofluoroalkane of at least 90 mole %. In another embodiment, thecatalytic fluorination of the fluoroolefin results in a percentconversion to the hydrofluoroalkane of at least 95%. In anotherembodiment, the catalytic fluorination of the fluoroolefin results in apercent conversion to the hydrofluoroalkane of at least 98%. In stillanother embodiment, the catalytic fluorination of the fluoroolefinresults in a percent conversion to the hydrofluoroalkane of at least99%.

An aspect of the invention is to replace step (ii) of the reaction formaking 1234yf described in the introduction with the present process.

One of the advantages of the present disclosure is that the catalyticreaction for hydrofluorination, as described herein, takes place atlower temperatures, much lower than other catalysts for the otherhydrofluorination reactions of fluoroolefin, such as SbCl₅ orfluorinated SbCl₅. Unlike these other catalysts, SbF₅ is a liquid atthese lower temperatures that are used in the present process.Therefore, less energy is required to conduct these hydrofluorinationreactions. In addition, in the present process, the catalyst hassubstantial activity at the lower temperature. Thus, the catalyticprocess proceeds at a low temperature, thereby making it more efficient.

In addition, another advantage is that the ratio of the desiredhydrofluoroalkane produced relative to the starting olefin is about 90:1or greater, and in another embodiment, is about 100:1 or greater and inanother embodiment is about 110:1 or greater. Thus, for another reason,this reaction is quite efficient.

Moreover, in view of the efficiency, if an olefin and the resultinghydrofluoroalkane from the hydrofluorination reaction, such as 1233xfand 244bb, were mixed together and reacted under the conditions of thepresent invention with SbF₅, additional hydrofluoroalkane product wouldbe formed. For example, in one embodiment, if the feed material ratio ofolefin, such as 1233xf, to hydrofluoroalkane, such a 244bb, is greaterthan about 1 mole %, the present process will significantly convert theunreacted olefin to hydrofluoroalkane, thereby increasing the amount ofthe hydrofluoroalkane in the mixture. The present disclosure thusprovides a method of maximizing the yield of the desiredhydrofluoroalkane relative to the olefin. Thus, in the above example,wherein the olefin is 1233xf and the hydrofluoroalkane is 244bb, if1233xf is present in greater than about 1 mole %, the resulting productwould have significantly more 244bb present than prior to the reaction.

Thus, in one embodiment, this advantage of the present disclosure can beused to improve the yield of HFO-1234yf being produced. As describedhereinabove, the preparation of HFO-1234yf may include at least threereaction steps, as follows:

(i) (CQ₂=CCl—CH₂Q or CQ₃-CCl═CH₂ orCQ₃-CHCl—CH₂Q)+HF→2-chloro-3,3,3-trifluoropropene (HCFO-1233xf)+HCl in avapor phase reactor charged with a solid catalyst;

(ii) 2-chloro-3,3,3-trifluoropropene(HCFO-1233xf)+HF→2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) in aliquid phase reactor charged with a liquid hydrofluorination catalyst;and

(iii) 2-chloro-1,1,1,2-tetrafluoropropane(HCFC-244bb)→2,3,3,3-tetrafluoropropene (HFO-1234yf) in a vapor phasereactor.

The general reactions of steps (i), (ii) and (iii) are well known in theart. For example, they are described in U.S. Pat. No. 8,846,990, thecontents of which are incorporated by reference.

In the first step, a starting composition, which comprises1,1,2,3-tetrachloropropene (HCO-1230xa or 1230xa), reacts with anhydrousHF in a first reactor (fluorination reactor) to produce a mixture of atleast HCFO-1233xf (2-chloro-3,3,3-trifluoropropene) and HCl. Thereaction is carried out in a reactor in the gaseous phase at atemperature of about 200° C. to about 400° C. and a pressure of about 0to about 200 psig. The effluent stream exiting in the vapor phasereactor may optionally comprise additional components, such asun-reacted HF, un-reacted starting composition, heavy intermediates,HFC-245cb, or the like.

This reaction may be conducted in any reactor suitable for a vapor phasefluorination reaction. The reactor may be constructed from materialswhich are resistant to the corrosive effects of hydrogen fluoride suchas Hastalloy, Inconel, Monel, and the like. In the case of a vapor phaseprocess, the reactor is filled with a vapor phase fluorination catalyst.Any fluorination catalysts known in the art may be used in this process.Suitable catalysts include, but are not limited to, metal oxides,hydroxides, halides, oxyhalides, inorganic salts thereof and theirmixtures, any of which may be optionally halogenated, wherein the metalincludes, but is not limited to, chromium, aluminum, cobalt, manganese,nickel, iron, and combinations of two or more thereof. Combinations ofcatalysts suitable for the present invention nonexclusively includeCr₂O₃, FeCl₃/C, Cr₂O₃/Al₂O₃, Cr₂O₃/AlF₃, Cr₂O₃/carbon,CoCl₂/Cr₂O₃/Al₂O₃, NiCl₂/Cr₂O₃/Al₂O₃, CoCl₂/AlF₃, NiCl₂/AlF₃ andmixtures thereof. Chromium oxide/aluminum oxide catalysts are describedin U.S. Pat. No. 5,155,082, the contents of which are incorporatedherein by reference. Chromium (III) oxides such as crystalline chromiumoxide or amorphous chromium oxide are preferred with amorphous chromiumoxide being most preferred. Chromium oxide (Cr₂O₃) is a commerciallyavailable material which may be purchased in a variety of particlesizes. Fluorination catalysts having a purity of at least 98% arepreferred. The fluorination catalyst is present in an excess but in atleast an amount sufficient to drive the reaction.

This first step of the reaction is not necessarily limited to a vaporphase reaction and may also be performed using a liquid phase reactionor a combination of liquid and vapor phases, such as that disclosed inU.S. Published Patent Application No. 2007/0197842, the contents ofwhich are incorporated herein by reference. It is also contemplated thatthe reaction can be carried out batch wise or in a continuous manner, ora combination of these.

For embodiments in which the reaction comprises a liquid phase reaction,the reaction can be catalytic or non-catalytic. Lewis acid catalysts,such as metal-halide catalysts, including antimony halides, tin halides,thallium halides, iron halides, and combinations of two or more ofthese, may be employed. In certain embodiments, metal chlorides andmetal fluorides are employed, including, but not limited to, SbCl₅,SbCl₃, SbF₅, SnCl₄, TiCl₄, FeCl₃ and combinations of two or more ofthese. It is noted that SbF₅ is a liquid at low temperature.

In the second step of the process for forming2,3,3,3-tetrafluoropropene, HCFO-1233xf is converted to HCFC-244bb. Inone embodiment, this step can be performed in the liquid phase in aliquid phase reactor, which may be TFE or PFA-lined. Such a process canbe performed in a temperature range of about 70° C. to about 120° C. andat a pressure ranging from about 50 to about 120 psig. Any liquid phasefluorination catalyst may be used that is effective at thesetemperatures. A non-exhaustive list includes Lewis acids, transitionmetal halides, transition metal oxides, Group IVb metal halides, GroupVb metal halides, or combinations thereof. Non-exclusive examples ofliquid phase fluorination catalysts are antimony halide, tin halide,tantalum halide, titanium halide, niobium halide, molybdenum halide,iron halide, fluorinated chrome halide, fluorinated chrome oxide orcombinations thereof. Specific non-exclusive examples of liquid phasefluorination catalysts are SbCl₅, SbCl₃, SbF₅, SnCl₄, TaCl₅, TiCl₄,NbCl₅, MoCl₆, FeCl₃, fluorinated species of SbCl₅, fluorinated speciesof SbCl₃, fluorinated species of SnCl₄, fluorinated species of TaCl₅,fluorinated species of TiCl₄, fluorinated species of NbCl₅, fluorinatedspecies of MoCl₆, fluorinated species of FeCl₃, or combinations thereof.

These catalysts can be readily regenerated by any means known in the artif they become deactivated. One suitable method of regenerating thecatalyst involves flowing a stream of chlorine through the catalyst. Forexample, from about 0.002 to about 0.2 lb per hour of chlorine can beadded to the liquid phase reaction for every pound of liquid phasefluorination catalyst. This may be done, for example, for from about 1to about 2 hours or continuously at a temperature of from about 65° C.to about 100° C.

This second step of the reaction is not necessarily limited to a liquidphase reaction and may also be performed using a vapor phase reaction ora combination of liquid and vapor phases, such as that disclosed in U.S.Published Patent Application No. 2007/0197842, the contents of which areincorporated herein by reference. To this end, the HCFO-1233xfcontaining feed stream is preheated to a temperature of from about 50°C. to about 400° C., and is contacted with a catalyst and fluorinatingagent. Catalysts may include standard vapor phase agents used for such areaction and fluorinating agents may include those generally known inthe art, such as, but not limited to, hydrogen fluoride.

In the process described in the art, such as that described in U.S.Published Patent Application No. 2007/0197842, the product from thesecond step is then transferred to a third reactor wherein the 244bb isdehydrohalogenated. The catalysts in the dehydrochlorination reactionmay be or comprise metal halide, halogenated metal oxide, neutral (orzero oxidation state) metal or metal alloy, or activated carbon in bulkor supported form. Metal halide or metal oxide catalysts may include,but are not limited to, mono-, bi-, and tri-valent metal halides, oxidesand their mixtures/combinations, and more preferably mono-, andbi-valent metal halides and their mixtures/combinations. Componentmetals of metal halides, oxides and their mixtures/combinations include,but are not limited to, Cr³⁺, Fe³⁺, gM²⁺, Ca²⁺, Ni²⁺, Zn²⁺, Pd²⁺, Li⁺,Na⁺, K⁺, and Cs⁺. Component halides include, but are not limited to, F,Cl, Br, and I. Examples of useful mono- or bi-valent metal halideinclude, but are not limited to, LiF, NaF, KF, CsF, MgF₂, CaF₂, LiCl,NaCl, KCl, and CsCl. Halogenation treatments can include any of thoseknown in the prior art, particularly those that employ HF, F₂, HCl, Cl₂,HBr, Br₂, HI, and I₂ as the halogenation source.

When the catalyst is or comprises a neutral, i.e., zero valent metal,then metals and metal alloys and their mixtures are used. Useful metalsinclude, but are not limited to, Pd, Pt, Rh, Fe, Co, Ni, Cu, Mo, Cr, Mn,and combinations of the foregoing as alloys or mixtures. The catalystmay be supported or unsupported. Useful examples of metal alloysinclude, but are not limited to, SS 316, Monel 400, Inconel 825, Inconel600, and Inconel 625. Such catalysts may be provided as discretesupported or unsupported elements and/or as part of the reactor and/orthe reactor walls.

Preferred, but non-limiting, catalysts include activated carbon,stainless steel (e.g., SS 316), austenitic nickel-based alloys (e.g.,Inconel 625), nickel, fluorinated 10% CsCl/MgO, and 10% CsCl/MgF₂. Asuitable reaction temperature is about 300° C. to about 550° C. and asuitable reaction pressure may be between about 0 psig to about 150psig. The reactor effluent may be fed to a caustic scrubber or to adistillation column to remove the byproduct of HCl to produce anacid-free organic product which, optionally, may undergo furtherpurification using one or any combination of purification techniquesthat are known in the art.

The dehydrohalogenation reaction is carried out in the vapor phase. Itmay be carried out at a temperature range of from about 200° C. to about800° C., from about 300° C. to about 600° C., or from about 400° C. toabout 500° C. Suitable reactor pressures range from about 0 psig toabout 200 psig, from about 10 psig to about 100 psig, or from about 20to about 70 psig.

A method of increasing the yield and conversion of 1233xf to 1234yf andto make the process more efficient is to react the product of step (ii),which contains a mixture of 1233xf and 244bb, with SbF₅ in accordancewith the process of the present invention prior to thedehydrochlorination step. This increases the amount of 244bb present(decreasing the amount of 1233xf present) and the resulting product canthen be subjected to step (iii) above. By conducting this additionalhydrofluorination reaction, more 244bb is produced, and as a result,significantly more 1234yf is produced. The 244bb thus produced is thentransferred to another reactor wherein it undergoes dehydrohalogenation,in accordance with step (iii).

Alternatively, as described above, instead of conducting step (ii) ofthe process, the 1233xf produced in step (i) is hydrofluorinated with HFin the presence of SbF5, in accordance with the present invention, asdescribed herein. The 244bb product thus formed is thendehydrochlorinated to form 1234yf, in accordance with step (iii)described hereinabove.

The following non-limiting examples further illustrate the invention.

EXAMPLES

Example 1-1233xf Hydrofluorination by HF with SbF₅ Catalyst at 30° C.

13.8 g of HF and 5 g of SbF₅ were loaded into a 210 mL shaker tubereactor. The reactor was then evacuated and chilled to −15° C. 30 g of1233xf was added into the reactor. The reactor was then heated to 30° C.with agitation. Once the temperature reached 30° C., water was added tothe reactor to quench the catalyst. The organic layer was vaportransferred into a stainless steel cylinder and analyzed by GC-MS. Table1 below shows the results of the GC-MS analysis.

TABLE 1 mol ratio mol % 1233xf/244bb 143a 0.005% 245cb 0.032% 245fa0.059% Unknown 0.001% 244bb 99.420% 0.48% 1233xf 0.474% 243ab 0.009%

Example 2-1233xf Hydrofluorination by HF with SbF₅ Catalyst at 10° C.

13.8 g of HF and 5 g of SbF₅ were loaded into a 210 mL shaker tubereactor. The reactor was then evacuated and chilled to −15° C. 30 g of1233xf was added into the reactor. The reactor was then heated to 10° C.with agitation. Once the temperature reached 10° C., water was added tothe reactor to quench the catalyst. The organic layer was vaportransferred into a stainless steel cylinder and analyzed by GC-MS. Table2 below shows the results of the GC-MS analysis.

TABLE 2 mol ratio Compounds mol % 1233xf/244bb 245cb  0.017% 245fa0.0200% 244bb 98.236% 1233xf  0.794% 0.81% 1233xf dimer  0.934%

Example 3-1233xf Hydrofluorination by HF with SbF₅ Catalyst at 30° C.

10.0 g of HF and 5 g of SbF₅ were loaded into a 210 mL shaker tubereactor. The reactor was then evacuated and chilled to −40° C. 30 g of1233xf was added into the reactor. The reactor was then heated to 30° C.with agitation and stirred for an hour. The reactor was chilled to −30°C. quickly and 75 mL of water was added to the reactor to quench thecatalyst. The organic layer was vapor transferred into a stainless steelcylinder and analyzed by GC-MS. Table 3 below shows the results of theGC-MS analysis.

TABLE 3 mol ratio Compound mol % 1233xf/244bb 245cb 14.412% 245fa 0.096%244bb 84.147% 1233xf 0.768% 0.91% 243ab 0.576%

Comparative Example 1—1233xf-244bb Equilibrium by HF with FluorinationSbCl₅ Catalyst at 80° C.

18.0 g of HF and 14.0 g of SbCl₅ were loaded into a 210 mL shaker tubereactor and heated at 100° C. for 2 hours with agitation. The reactorwas then evacuated and chilled to 0° C. to vent off HCl. 20 g of 244bb(99.7 mol %) was added into the reactor. The reactor was then heated to80° C. for an hour and then quickly chilled to 30° C. Water was added tothe reactor to quench the catalyst. The organic layer was vaportransferred into a stainless steel cylinder and analyzed by GC-MS. Table4 below shows the results of the GC-MS analysis. The 1233xf/244bb ratioincreased to 1.95 mol % from 0.3 mol %. This indicates the existence ofequilibrium between 1233xf and 244bb which prevents the full conversionof 1233xf to 244bb.

TABLE 4 mol ratio mol % 1233xf/244bb 245cb 0.089% 244bb 92.907% 1233xf1.815% 1.95% 243ab 4.905% Others 0.284%

Many aspects and embodiments have been described and are merelyexemplary and not limiting. After reading the specification, skilledartisans appreciate that other aspects and embodiments are possiblewithout departing from the scope of the invention.

Other features and benefits of any one or more of the embodiments willbe apparent from the hereinabove detailed description and the claims.

1. A hydrofluoroalkane composition formed by reacting HF with olefin ofthe formula RCX═CYZ in the liquid phase in the presence of a catalyst,the catalyst being SbF₅, at a temperature ranging from about −30° C. toabout 65° C. to produce a hydrofluoroalkane having the formula; whereinX, Y and Z are independently the same or different and are H, F, or Cl,and R is trifluoromethyl and the hydrofluoroalkane composition comprisesgreater than 95% RCXFCHYZ.
 2. The hydrofluoroalkane composition of claim1, wherein the hydrofluoroalkane composition comprises greater than 98%RCXFCHYZ.
 3. The hydrofluoroalkane composition of claim 1, wherein thehydrofluoroalkane composition comprises greater than 99% RCXFCHYZ. 4.The hydrofluoroalkane composition of claim 1, wherein thehydrofluoroalkane is 2-chloro-1,1,1,2-tetrafluoropropane.
 5. Thehydrofluoroalkane composition of claim 1, wherein the olefin is2-chloro-3,3,3-trifluoropropene and the hydrofluoroalkane is2-chloro-1,1,1,2-tetrafluoropropane.
 6. The hydrofluoroalkanecomposition of claim 1, wherein the hydrofluoroalkane compositioncomprises greater than 98% 1,1,1,3,3-pentafluoropropane.
 7. Thehydrofluoroalkane composition of claim 1, wherein the hydrofluoroalkanecomposition comprises greater than 99% 1,1,1,3,3-pentafluoropropane. 8.The hydrofluoroalkane composition of claim 4, wherein the temperature isfrom about −30° C. to about 25° C.
 9. The hydrofluoroalkane compositionof claim 8, wherein the temperature is from about 5° C. to about 25° C.10. A method for preparing 2,3,3,3-tetrafluoro-l-propene comprisingpreparing reacting the hydrofluoroalkane composition of claim 4 in avapor phase reactor to form 2,3,3,3-tetrafluoro-1-propene.
 11. Ahydrofluoroalkene composition formed by the reacting thehydrofluoroalkane composition of claim 4 in a vapor phase reactor toform 2,3,3,3-tetrafluoro-1-propene.
 12. The hydrofluoroalkanecomposition of claim 1, wherein the olefin is 1,3,3,3-tetrafluoropropeneand the hydrofluoroalkane is 1,1,1,3,3-pentafluoropropane.
 13. Thehydrofluoroalkane composition of claim 1, wherein the olefin is (Z)- or(E)-1-chloro-3,3,3-trifluoropropene, and the hydrofluoroalkane is3-chloro-1,1,1,3-tetrafluoropropane.
 14. The hydrofluoroalkanecomposition of claim 1, wherein the olefin is1-chloro-2,3,3,3-tetrafluoropropene and the hydrofluoroalkane is1,1,1,2,2-pentafluoro-3-chloropropane or1,1,1,2,3-pentafluoro-3-chloropropane.
 15. The hydrofluoroalkanecomposition of claim 1, wherein the olefin is 2,3,3,3-tetrafluoropropeneand the hydrofluoroalkane is 1,1,1,2,2-pentafluoropropane.
 16. Ahydrofluoroalkane composition formed by reacting HF with an olefincomprising at least one member selected from the group consisting of2-chloro-3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene,chlorotetrafluoropropenes, 2,3,3,3-tetrafluoropropene,1,3,3,3-tetrafluoropropene, and 3,3,3-trifluoropropene in the liquidphase in the presence of a catalyst at a temperature ranging from about−30° C. to about 40° C. to produce the hydrofluoroalkane; wherein thehydrofluoroalkane composition comprises greater than 95% RCXFCHYZ,wherein X, Y and Z are independently the same or different and are H, F,or Cl, and R is trifluoromethyl.
 17. The hydrofluoroalkane compositionof claim 16, wherein the hydrofluoroalkane composition comprises greaterthan 98% RCXFCHYZ.
 18. The hydrofluoroalkane composition of claim 16,wherein the hydrofluoroalkane composition comprises greater than 99%RCXFCHYZ.
 19. The hydrofluoroalkane composition of claim 16, wherein thetemperature is from about −30° C. to about 25° C.
 20. A method forpreparing 2,3,3,3-tetrafluoro-l-propene comprising preparing reactingthe hydrofluoroalkane composition of claim 15 in a vapor phase reactorto form 2,3,3,3-tetrafluoro-1-propene.
 21. A hydrofluoroalkenecomposition formed by the reacting the hydrofluoroalkane composition ofclaim 4 in a vapor phase reactor to form 2,3,3,3-tetrafluoro-1-propene.22. A hydrofluoroalkene composition formed by reacting2-chloro-1,1,1-trifluoropropene with HF in a liquid phase reactorcharged with a hydrofluorination catalyst at a reaction temperatureabove 65° C. to produce a mixture of 2-chloro-1,1,1-trifluoropropene and2-chloro-1,1,1,2-tetrafluoropropane; reacting HF with said mixture inthe liquid phase in the presence of SbF5 at a temperature ranging fromabout 30° C. to about 65° C. to further react the unconverted2-chloro-1,1,1-trifluoropropene to form additional2-chloro-1,1,1,2-tetrafluoropropane and dehydrohalogenating2-chloro-1,1,1,2-tetrafluoropropane in a vapor phase reactor with orwithout a catalyst to form 2,3,3,3-tetrafluoro-1-propene.